Manganese-tertiary phosphine-polymer complexes

#The present invention relates to novel polymer compositions useful in reversibly complexing with gases such as oxygen, hydrogen, sulfur dioxide, alkenes, carbon monoxide and the like. The present invention further comprehends a novel method by which the polymer compositions can be synthesized.

#It is known that certain metal complexes take up gases to form adducts from which the gases can be recovered. The Cobalt (II) complex known as the Salen Chelate and related Fluomine chelate complexes of the Vaska type, in which the metal is iridium, ruthenium, osmium or rhodium, take up oxygen reversibly. Under moderate conditions the adducts do not however release oxygen to regenerate the sorbent complexes sufficiently readily to enable oxygen to be produced or nitrogen to be purified on a commercial scale.

#It is also known that certain chemical complexes will reversibly complex with gases. In particular McAuliffe et al, in the U.S. Pat. No. 4,251,452 disclose and claim certain manganese-tertiary phosphine complexes useful in the separation of a gas such as oxygen, hydrogen, sulfur dioxide, alkenes and carbon monoxide from a fluid comprising the gas.

#The following specific example will show by way of illustration and not by way of limitation, the use of the novel method and apparatus of the present invention.

#It has been noted that the synthesis procedures of the present invention are best carried out employing anhydrous starting materials. Example 1 describes the drying and handling techniques employed to secure and maintain the starting materials in an anhydrous state. Examples 2 and 3 describe preparations of manganese (II) heme-like polymeric films prepared in situ from PVC and silicone.

#Anhydrous manganese halides (Mn X.sub.2, X=Cl, Br, or I) can be prepared by heating the commercial hydrated salts in vacuo at 150.degree.-300.degree. C./l mm Hg for 12 hours. The products are pale pink solids which are powdered and manipulated in a dry box (they rapidly absorb moisture from air). Manganese thiocyanate can be prepared from manganese sulphate and barium thiocyanate and recrystallized from alcohol. The thiocyanate can be dried as described above for manganese halides. Tetrahydrofuran dried by refluxing over sodium wire, and freshly distilled from sodium benzophenone ketyl under nitrogen.